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A four-component relativistic perspective on an E ⊗ e Jahn-Teller model
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0002-6143-0480
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Applied Physical Chemistry. School of Chemistry, University of Birmingham, Birmingham, B15 2TT, United Kingdom.ORCID iD: 0000-0002-0246-3995
2026 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 164, no 2Article in journal (Refereed) Published
Abstract [en]

Most advances in electronic spin-dependent non-adiabatic dynamics focus on refining the underlying dynamics methods. In contrast, this work considers an improved description of spin-orbit coupling by explicitly accounting for its relativistic origins. To this end, we extend a standard one-electron triatomic Jahn-Teller model to the four-component relativistic domain. In our formulation, the electron is treated using the Dirac-Coulomb Hamiltonian, while the nuclei remain non-relativistic, departing from the conventional formulation that incorporates the Pauli spin-orbit coupling as a perturbation. The most striking difference between our relativistic model and the conventional one is the presence of vibronic coupling terms on the anti-diagonal of the diabatic potential matrix. These terms scale as 1/c2 and, although nominally small, they can be amplified near avoided-crossings or in systems with heavy nuclei. Furthermore, their presence implies that nuclear motion can affect the direction of the electron spin, a feature entirely absent in the non-relativistic formulation of our model. In the adiabatic representation, the couplings translate to non-Abelian characteristics of the non-adiabatic coupling matrix that persist even in the Born-Oppenheimer approximation. Within our model setting, a relativistic formulation allows for a more intricate interplay between the electronic spin and nuclear degrees of freedom.

Place, publisher, year, edition, pages
AIP Publishing , 2026. Vol. 164, no 2
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-375915DOI: 10.1063/5.0304011ISI: 001659412100001PubMedID: 41511031Scopus ID: 2-s2.0-105027115665OAI: oai:DiVA.org:kth-375915DiVA, id: diva2:2032978
Note

QC 20260128

Available from: 2026-01-28 Created: 2026-01-28 Last updated: 2026-01-28Bibliographically approved

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van Horn, MartinHolmgaard List, Nanna

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